Lithium argyrodite

ABSTRACT

The invention relates to lithium argyrodite of the general formula (I): Li +   (12-n-x) B n+ X 2−   6-x Y −   x (I), where B n+  is selected from the group P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb, and Ta, X 2−  is selected from the group S, Se, and Te, Y −  is selected from the group Cl, Br, I, F, CN, OCN, SCN, N 3 , and where 0≦x≧2, and a method for the production thereof, and the use thereof as a lithium-ion electrolyte in primary and secondary electrochemical energy storage.

The present invention relates to a novel class of lithium-rich solid-state compounds, a process for their preparation and their use as solid electrolytes in primary and secondary electrochemical energy stores.

Argyrodites have long been known and are derived from argyrodite Ag₈GeS₆, which was described for the first time in 1886 by C. Winkler and the analysis of which led to the discovery of germanium. The argyrodite family consists of more than 100 crystalline solids and includes, for example, those solid-state compounds in which the silver is replaced by copper, the germanium by gallium or phosphorus and the sulfur by selenium. Thus, Nitsche, Kuhs, Krebs, Evain, Boucher, Pfitzner and Nilges describe, inter alia, compounds such as Cu₉GaS₆, Ag₇PSe₆ and Cu₈GaS₅Cl, the solid-state structures of which are derived from argyrodite.

Li argyrodites were unknown for a long time, with the exception of the insufficiently characterized compound Li₇PS₆ (J. F. Brice, C. R. Seances in Acad. Sci. 1976, C283, 581). Recent investigations, for example by Eckert, Zhang and Kennedy in Chem. of Mat. 1990, 2, 273-279, relate to thermomechanical optimization experiments for the Li₂S—P₂S₅ system and show as a whole samples which do not have a single phase. However, signs of high lithium mobility are found for this system in many samples.

More detailed investigations have, however, shown that the production of single-phase solids in the Li₂S—P₂S₅ system is difficult and is greatly dependent, inter alia, on the starting materials and crucible materials used during the preparation, so that different byproducts form depending on the material used.

It is therefore an object of the present invention to provide a novel class of lithium-rich solid-state compounds which permit single-phase preparation in addition to high lithium ion mobility.

This object is achieved, according to the invention, by lithium argyrodites of the general formula (I):

Li⁺ _((12-n-x))B^(n+)X²⁻ _(6-x)Y⁻ _(x)   (I)

in which

B^(n+) is selected from the group consisting of P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb and Ta,

X²⁻ is selected from the group consisting of S, Se and Te,

Y⁻ is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, N₃, and in which 0≦x≦2.

Advantageously, the inventive class of novel lithium-rich argyrodites permits preparation of single-phase solids. In addition, the inventive compounds of the novel class have high lithium ion mobility, which can preferably be employed in a use as solid electrolyte. In contrast to known lithium electrolytes, the lithium argyrodites according to the invention can be used in a wide temperature range from −150° C. to 600° C. Thus, the temperature sensitivity of electrochemical energy stores which has been observable to date can be reduced.

The component B^(n+) can preferably be selected from the group consisting of P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb and Ta. P, As, Sb and Ga are particularly preferred, especially with regard to use as an electrolyte constituent of a lithium accumulator.

The component X²⁻ can be selected from the group consisting of S, Se and Te. In particular, components X²⁻ selected from the group consisting of S and Se are favored in a preferred configuration of the invention, owing to their easier preparation.

The component Y⁻ can preferably be selected from the group consisting of Cl, Br, I, F, OCN, SCN, N₃, CN. Cl, Br and I are particularly preferred, especially with regard to use as an electrolyte constituent of a lithium accumulator.

The lithium argyrodites according to the invention can preferably be compounds of the general formula (II):

Li₆PS₅Z   (II),

in which the constituent Z may be a monovalent anion selected from the group consisting of the halides and the pseudohalides.

In a further preferred embodiment of the present invention, the component Z can be selected from the group consisting of Cl, Br, I.

Particularly when Z═I, these compounds show a high specific Li⁺ ion conductivity, in said case Z═I of about 7×10³ Scm⁻¹ at room temperature. NMR investigations on these compounds have also indicated a high specific Li⁺ mobility.

The compounds of the formula (II) where Z═Cl, Br or I can advantageously be prepared in a solid-state synthesis, for example according to the following reactions:

6 Li₂S+2 P+½ S₈+I₂→2 Li₆PS₅I

5 Li₂S+2 P+⅝ S₈+2 LiBr→2 Li₆PS₅Br

5 Li₂S+2 P+⅝ S₈+2 LiCl→2 Li₆PS₅Cl

In a further preferred embodiment of the invention, the lithium argyrodites can be compounds of the general formula (III):

Li₆B⁶⁺S_(5-a)X²⁻ _(a)Y⁻  (III)

in which

B⁶⁺ is selected from the group consisting of P, As and Sb,

X²⁻ is selected from the group consisting of Se and Te,

Y⁻ is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, N₃, and in which 0≦a≦2.

Furthermore preferred are inventive lithium argyrodites of the general formula (IV):

Li₇B⁶⁺S_(6-a)X²⁻ _(a)   (IV)

in which

B⁶⁺ is selected from the group consisting of P, As and Sb,

X²⁻ is selected from the group consisting of Se and Te, and in which 0≦a≦2.

The invention moreover relates to a process for the preparation of lithium argyrodites of the general formula (I), characterized by the steps:

-   -   mixing of the stoichiometric amounts of the starting substances         under an inert gas atmosphere,     -   pressing of the resulting powder mixture to give pellets, and     -   heating of the pellets to temperatures from 400° C. to 700° C.         for a duration of from 3 days to 10 days.

According to the invention, a process which permits a simple procedure in addition to a good single-phase character of the crystalline compounds can advantageously be provided.

The process according to the invention can be carried out in particular at a temperature of from 500° C. to 600° C., preferably at 550° C.

In a further advantageous embodiment of the process, a duration of from 4 days to 8 days, preferably a duration of 7 days, can be provided.

An inventive lithium argyrodite of the general formula (I) can preferably be used as a lithium ion electrolyte for primary and secondary electrochemical energy stores.

The invention is described further by the following examples without being limited thereto.

EXAMPLES 1. Preparation of the Compound Li₆PS₅I According To the Invention

For the preparation of the compound Li₆PS₅I, the starting materials I₂, S₈, Li₂S and P₂S₅ were weighed out in the stoichiometric ratio under an argon inert gas atmosphere, transferred to a graphitized quartz ampoule and melted in vacuo. The sample was heated in a tubular furnace at a temperature of 550° C. for 6 days and then slowly cooled. Single-phase crystals of the compound Li₆PS₅I were obtained as a white solid.

2. Preparation of the Compound Li₆PS₅Br According To the Invention

For the preparation of the compound Li₆PS₅Br, the starting materials LiBr, Li₂S and P₂S₅ were weighed out in the stoichiometric ratio under an argon inert gas atmosphere, transferred to a graphitized quartz ampoule and melted in vacuo. The sample was heated in a tubular furnace at a temperature of 550° C. for 6 days and then slowly cooled. Single-phase crystals of the compound Li₆PS₅Br were obtained as a white solid.

3. Preparation of the Compound Li₆PS₅Cl According To the Invention

For the preparation of the compound Li₆PS₅Cl, the starting materials LiCl, Li₂S and P₂S₅ were weighed out in the stoichiometric ratio under an argon inert gas atmosphere, transferred to a graphitized quartz ampoule and melted in vacuo. The sample was heated in a tubular furnace at a temperature of 550° C. for 6 days and then slowly cooled. Single-phase crystals of the compound Li₆PS₅Cl were obtained as a white solid.

4. Preparation of the Compound Li₇PS₅Se According To the Invention

For the preparation of the compound Li₇PS₅Se, the starting materials S₈, Li₂S and P₂Se₅ were weighed out in the stoichiometric ratio under an argon inert gas atmosphere, transferred to a graphitized quartz ampoule and melted in vacuo. The sample was heated in a tubular furnace at a temperature of 500° C.-550° C. for 6 days and then slowly cooled. Single-phase crystals of the compound Li₇PS₅Se were obtained as a white solid. 

1. A lithium argyrodite of the general formula (I): Li⁺ _((12-n-x))B^(n+)X²⁻ _(6-x)Y⁻ _(x)   (I) in which B^(n+) is selected from the group consisting of P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb and Ta, X²⁻ is selected from the group consisting of S, Se and Te, Y⁻ is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, N₃, and in which 0≦x≦2.
 2. The lithium argyrodite as claimed in claim 1, characterized in that the component B^(n+) is selected from the group consisting of P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb and Ta, and preferably from the group consisting of P, As and Ga.
 3. The lithium argyrodite as claimed in claim 1, characterized in that the component X²⁻ is selected from the group consisting of S, Se and Te, and preferably from the group consisting of S and Se.
 4. The lithium argyrodite as claimed in claim 1, characterized in that the component Y⁻ is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, N₃, and preferably from the group consisting of Cl, Br and I.
 5. The lithium argyrodite as claimed in claim 1, characterized in that it is a compound of the general formula (II): Li₆PS₅Z   (II) in which the constituent Z a monovalent anion selected from the group consisting of the halides and pseudohalides.
 6. The lithium argyrodite as claimed in claim 5, characterized in that the component Z is selected from the group consisting of Cl, Br and I.
 7. The lithium argyrodite as claimed in claim 1, characterized in that it is a compound of the general formula (III): Li₆B⁶⁺S_(5-a)X²⁻ _(a)Y⁻  (III) in which B⁶⁺ is selected from the group consisting of P, As and Sb, X²⁻ is selected from the group consisting of Se and Te, Y⁻ is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, N₃, and in which 0≦a≦2.
 8. The lithium argyrodite as claimed in claim 1, characterized in that it is a compound of the general formula (IV): Li₇B⁶⁺S_(6-a)X²⁻ _(a)   (IV) in which B⁶⁺ is selected from the group consisting of P, As and Sb, X²⁻ is selected from the group consisting of Se and Te, and in which 0≦a≦2.
 9. A process for the preparation of a lithium argyrodite of the general formula (I), characterized by the steps: mixing of the stoichiometric amounts of the starting substances under an inert gas atmosphere, pressing of the resulting powder mixture to give pellets, and heating of the pellets to temperatures from 400° C. to 700° C. for a duration of from 3 days to 10 days.
 10. The process for the preparation of a lithium argyrodite as claimed in claim 9, characterized in that temperatures of from 500° C. to 600° C., preferably of 550° C., are established.
 11. The process for the preparation of a lithium argyrodite as claimed in claim 9, characterized in that the heating is carried out for a duration of from 4 days to 8 days, preferably for 7 days.
 12. The use of a lithium argyrodite as claimed in claim 1 as a lithium ion electrolyte in primary and secondary electrochemical energy stores.
 13. The lithium argyrodite as claimed in claim 2, characterized in that the component X²⁻ is selected from the group consisting of S, Se and Te, and preferably from the group consisting of S and Se.
 14. The lithium argyrodite as claimed in claim 2, characterized in that the component Y⁻ is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, N₃, and preferably from the group consisting of Cl, Br and I.
 15. The lithium argyrodite as claimed in claim 3, characterized in that the component Y⁻ is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, N₃, and preferably from the group consisting of Cl, Br and I.
 16. The lithium argyrodite as claimed in claim 13, characterized in that the component Y⁻ is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, N₃, and preferably from the group consisting of Cl, Br and I.
 17. The lithium argyrodite as claimed in claim 2, characterized in that it is a compound of the general formula (II): Li₆PS₅Z   (II) in which the constituent Z a monovalent anion selected from the group consisting of the halides and pseudohalides.
 18. The lithium argyrodite as claimed in claim 3, characterized in that it is a compound of the general formula (II): Li₆PS₅Z   (II) in which the constituent Z a monovalent anion selected from the group consisting of the halides and pseudohalides.
 19. The lithium argyrodite as claimed in claim 4, characterized in that it is a compound of the general formula (II): Li₆PS₅Z   (II) in which the constituent Z a monovalent anion selected from the group consisting of the halides and pseudohalides.
 20. The lithium argyrodite as claimed in claim 14, characterized in that it is a compound of the general formula (II): Li₆PS₅Z   (II) in which the constituent Z a monovalent anion selected from the group consisting of the halides and pseudohalides. 